1. Biodiesel production from oils containing high content of water and FFA using zinc lanthanum mixture oxides as catalyst Shuli Yan 2008-02-18

2. Outline Introduction Experiments Results and Discussion Biodiesel Oils used in traditional processes for biodiesel production Homogeneous catalysts for biodiesel production Catalytic activity of Zn and La mixture oxides Effect of FFA addition on transesterfication Effect of water addition on transesterfication Catalyst structure and their effects on biodiesel production

3. Introduction Biodiesel Biodegradable Low emission profile Low toxicity Better fuel Efficiency High lubricity

4. Oils used in traditional processes for biodiesel production Food grade vegetable oils( soybean oil $2.03/gal, $0.27/lb) FFA content is lower than 0.5 % (wt) Water content is lower than 0.06% (wt) Introduction Crude oils and yellow grease( about 50 % of food oil) FFA content is in the range of 0.5 ~ 15 % (wt) Water content is higher than 0.06% (wt) Therefore:

6. Introduction Prices of some inexpensive materials ( Rudeck, 2000 ) BulkPrice range (per pound)Average price Animal/livestock feed $0.09 – $0.14 $0.12 Tallow $0.10 – $0.20 $0.17 Grease $0.07 – $0.20 $0.16

7. Introduction Negative effects of FFA and water in homogeneous catalysis for biodiesel production Saponification of FFA with alkaline catalysts Hydrolysis of triglyceride

8. Introduction Difficulties in phase separation A lot of washing water Environmental unfriendly Therefore: Developing a heterogeneous catalyst Homogeneous catalysts for biodiesel production

9. Simultaneous transesterification and esterification Minimizing hydorlysis and saponification  Developing a heterogeneous catalyst with high activity  Processing feedstocks with high content of FFA and water Our goal

10. Experiments Catalyst preparation and characterization Homogeneous-coprecipitation method using urea as precipitant 1.Prepare a mixture solution of Zn(NO 3 ) 2, La(NO 3 ) 3 and urea 2.Heat to 100 o C and hold for 6 hr 3.Stirred with magnetic stirrer 4.Filter/unfilter 5.Dry at 150 o C for 8 hr 6.Use step-rise calcination method at 250 (2hr), 300 (2hr), 350 (2hr), 400 (2hr), 450 o C (8hr), SEM/EDS, XRD, XPS, FT-IR Zn:La 1:0 1:1 3:1 9:1 0:1 Pure ZnO, Zn1La1, Zn3La1, Zn9La1, Pure La 2 O 3

11. Experiments Transesterification Molar ratio of methanol to soybean oil-----------------42:1 Catalyst dosage-------- ------------2.3 %(wt) Stir speed-------------- --------------490 rpm

12. Experiments FAME yield Water content FFA content Clarus 500 GC-MS, Perkin-Erlmer 831 KF Coulometer 809 KF Coulometer

13. Results and discussion Catalytic activity of zinc lanthanum metal oxides for transesterification Figure 1 Catalytic activity of metal oxides at different reaction temperatures Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, stir speed is 490 rpm; using step-rising heat method to control the reaction temperature; heating speed is 2 o C/min, and hold at the target temperature for 1 min.

14. Results and discussion Figure 2 Transesterification results of Zn3La1 at different temperatures Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, stir speed is 490 rpm;

15. Results and discussion Figure 3 Effect of catalyst composition on transesterification Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, reaction temperature is 200 oC stir speed is 490 rpm;

16. Results and discussion Effect of FFA addition on transesterification Figure 4 Yield of FAME in the presence of different FFA addition Reaction conditions: molar ratio of methanol to oil is 42:1, catalyst dosage is 2.3 (wt)%, reaction temperature is 200 oC, stir speed is 490 rpm; FFA content in refined oil: 0.02 %

17. Results and discussion Figure 5 Effect of FFA content on equilibrium yield of FAME of the transesterification processes Reaction conditions: 1. Acidic catalysis process, sulfuric acid amount is 3 %, molar ratio of methanol to oil is 6:1, reaction temperature is 60 o C, and reaction time is 96 hr. 2. Alkaline catalysis process, KOH amount is 1 %, molar ratio of methanol to oil is 6:1, reaction temperature is 25 o C, and reaction time is 8 hr. 3. Heterogeneously catalytic process, catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 o C, and reaction time is 1.5 hr.

18. Results and discussion Effect of water addition on transesterification Figure 6 Yield of FAME in the presence of different water addition Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 o C, stir speed is 490 rpm; Water content in refined oil is 0.0229 %, in methanol is 0.0191 %.

19. Results and discussion Figure 7 Effect of water content on equilibrium yield of FAME of the transesterification processes Reaction conditions: 1. Acidic catalysis process, sulfuric acid amount is 3 %, molar ratio of methanol to oil is 6:1, reaction temperature is 60 o C, and reaction time is 96 hr. 2. Alkaline catalysis process, KOH amount is 1 %, molar ratio of methanol to oil is 6:1, reaction temperature is 25 o C, and reaction time is 8 hr. 3. Heterogeneously catalytic process, catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 o C, and reaction time is 145 min.

20. Results and discussion Using oils containing high content of water and FFA in transesterification for biodiesel production Figure 8 Using oils containing high content of water and FFA for biodiesel production Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 o C, stir speed is 490 rpm;

21. Results and discussion Effect of catalyst structure on transeseterification XRD, SEM/EDS, XPS, FT-IR a.High specific surface area, multiporous structure, uniform bulk phase structure. b. Both acidic and basic sites exist on the surface of catalyst, and they participate in the formation of FAME. c. Active centre for transesterification (Effect of basic sites on transesterification) d.Active centre for esterification (Effect of acidic sites on esterfication) e.Catalytic ability of zinc lanthanum mixture oxides to hydrolysis reaction when oils containing high content of water

22. Results and discussion SEM/EDS

25. Results and discussion FFA Esterification in the presence of oil Figure 9 TAN changes during the process using refined oil with 5 % FFA addition Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm, FFA addition is about 5 %;

26. Results and discussion Figure 10 water content changes during the processes using refined oil with 5 % water addition and without water addition Reaction conditions: catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm, water content in oil is about 5.2 (wt)% catalyst amount is 2.3 (wt)%, molar ratio of methanol to oil is 42:1, reaction temperature is 200 oC, stir speed is 490 rpm, water content in oil is about 0.9 (wt)%

27. Results and discussion Reaction pathway for FAME formation when using oils with a high content of FFA and water × × × ×

28. ThankYou